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EP1383775B1 - Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung - Google Patents

Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung Download PDF

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EP1383775B1
EP1383775B1 EP02766889A EP02766889A EP1383775B1 EP 1383775 B1 EP1383775 B1 EP 1383775B1 EP 02766889 A EP02766889 A EP 02766889A EP 02766889 A EP02766889 A EP 02766889A EP 1383775 B1 EP1383775 B1 EP 1383775B1
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metal
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sbus
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EP1383775A1 (de
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Omar M. Yaghi
Mohamed Eddaoudi
Hailian Li
Jaheon Kim
Nathaniel Rosi
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University of Michigan System
University of Michigan Ann Arbor
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates generally to metal-organic frameworks, and more specifically to such frameworks, which are reticulated into a predetermined porous material with a tailored pore size and/or functionality, and their application as sorbents for storing gases such as methane.
  • Porous materials are mainly used for gas/liquid separation, catalysis, luminescence-based sensors, and gas storage. To achieve a specific application, a porous material with a defined pore size and function is needed. To achieve these challenging objectives, many scientists have devoted their knowledge and programs to develop this area.
  • a stable, porous metal-organic framework was disclosed recently. See Li, Hailian, Mohamed Eddaoudi, M. O'Keeffe and O.M. Yaghi, "Design and synthesis of an exceptionally stable and highly porous metal-organic framework," Nature, Vol. 402, pp. 276-279 (18 November 1999).
  • This framework was formed by diffusing triethylamine into a solution of zinc (II) nitrate and H 2 BDC (benzenedicarboxylic acid) in N,N'-dimethyl-formamide/chlorobenzene. This resulted in the deprotonation of H 2 BDC and its reaction with Zn 2+ ions.
  • the rendered cubic crystals were designated metal-organic framework (MOF)-5 and were found to comprise an extended, porous network having a three-dimensional intersecting channel system with 12.94 ⁇ spacing between centers of adjacent clusters.
  • MOF-5 crystalline structure described in Nature , supra has desirable characteristics, the process for making the structure actually renders a mixture of crystalline structures, the MOF-5 being a relatively low percentage of the mix. Further, the Nature MOF-5 structure appears to be limited to a single benzene ring as a linkage between adjacent Zn 4 (O)O 12 C 6 clusters.
  • W09905151 discloses a solid product which is a porous chiral (10,3)-a network of 1,3,5-benzenetricarboxylate molecules.
  • expanded structures have been formed using long links to increase the spacing between vertices in a net, yielding void space proportional to the length of the linker.
  • expanded structures provide for large pores (and one would therefore expect a high porosity), in practice they are often found to be highly undesirably interpenetrated and to have low porosity.
  • the present invention addresses and solves the above-mentioned problems by providing an isoreticular metal-organic framework (IRMOF), consisting essentially of a plurality of secondary building units (SBUs), each of the plurality of SBUs comprising an M 4 O(CO 2 ) 6 cluster; and a compound linking adjacent SBUs, the linking compound comprising a linear ditopic carboxylate having at least one phenyl group and at least one functional group X attached to the at least one phenyl group.
  • the inventive IRMOF has a substantially permanent porosity and is stable, with or without the presence of guest molecules.
  • a method of forming the inventive isoreticular metal-organic framework comprises the step of dissolving at least one metal salt and at least one linear ditopic carboxylate in a solvent to form a solution.
  • the solution is then crystallized to form the IRMOF.
  • the crystallizing step is carried out by at least one of: leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and transferring the solution to a closed vessel and heating to a predetermined temperature.
  • the selected conditions are ideal to form the cluster M 4 O(CO 2 ) 6 (the SBU).
  • the SBUs in the case of IRMOFs occupy the corners of the cube, and ditopic linkers link them.
  • member(s) of the IRMOFs series have been found to have very high methane storage capacity.
  • the inventive IRMOF(s) have been found to have a methane storage capacity of about 155 cm3/cm3, which is the highest methane storage capacity in any crystalline porous material to date.
  • the present invention is predicated upon the unexpected and fortuitous discovery that an extremely stable (with or without the presence of guest molecules within the pores of the framework) and highly (substantially permanently) porous isoreticular metal-organic framework having a topology similar to that shown in Figure 1 may be formed, even when utilizing linkers other than benzenedicarboxylate.
  • the links in Figure 1 are single, unsubstituted benzene rings.
  • the benzene ring of the dicarboxylate may be substituted with a functional group and/or the link may comprise a plurality of benzene rings (forming a horizontal line, a vertical line, or both, ie. the plurality of rings may be as tall as desired and/or as fat as desired), while retaining a stable network with very high porosity and substantially no undesirable interpenetration.
  • the present invention discloses the first series of tailored porous materials.
  • Iso -reticular Metal-Organic Frameworks are important avenues toward consistently and efficiently (with a high yield) rendering stable, substantially permanently porous materials having a predetermined characterization.
  • "Reticular” is an adjective defined in Random House Webster Unabridged Dictionary as "having the form of a net; netlike.” Isoreticular can thus be defined as: having the same network topology.
  • MOFs are formed by a combination of metal cations and polydentate organic linkers.
  • the incorporation of organic linkers as an integral part into the framework is of great advantage due to the ability to apply all the well-established organic chemistry knowledge to functionalize the linker.
  • the present invention shows that it is possible to design porous materials, "IRMOFs,” with tailored pores sizes and functionality/ies, an unprecedented achievement to date.
  • the starting building blocks have the relevant attributes necessary to assemble into the skeleton of the desired structure, (b) the synthesis be adaptable to using derivatives of those building blocks to produce structures with the same skeleton but different functionalities and dimensions, and importantly, (c) the products should be highly crystalline to allow the full characterization of their atomic connectivity by X-ray diffraction techniques.
  • MOF-5 The most notable example of a truly porous metal-organic frameworks (MOF) is MOF-5 in which octahedral Zn-O-C clusters are linked by benzene struts to reticulate into a primitive cubic structure (Fig. 1).
  • the exceptional rigidity and high porosity of MOF-5 led to its use as a target in studies aimed at overcoming the three challenges outlined immediately hereinabove and also to developing the next phase of this chemistry, namely, functionalization of the pores and systematic variation of their size--aspects that are highly sought after in solid-state chemistry and only recently pursued in crystalline zeolite research. See C.W. Jones, K. Tsuji and M.E. Davis, Nature 393 , 52 (1998).
  • a specific metal salt and a linear ditopic carboxylate were dissolved in a predefined solvent.
  • the mixture can either be left at room temperature to crystallize, and/or if necessary or desired, a diluted base is added or allowed to diffuse into the mixture to initiate the reaction, and/or transferred to a closed vessel and heated to a predetermined, precise temperature.
  • the selected conditions are ideal to form the cluster M 4 O(CO 2 ) 6 (also called a secondary building unit (SBU)).
  • SBU secondary building unit
  • the SBU in the case of IRMOFs occupy the corners of the cube, and ditopic linkers link them.
  • the resultant dimension, pore size and free volume are related to linkers: Expanded structure results from expanding the linker to a series of linearbenzene rings, and reducing the pore volume is generated by introducing functional groups on the benzene rings (those pointing toward the inner cavities).
  • An isoreticular metal-organic framework according to the present invention consists essentially of a plurality of secondary building units (SBUs), each of the plurality of SBUs comprising an M 4 O(CO 2 ) 6 cluster.
  • a compound links adjacent SBUs, the linking compound comprising a linear ditopic carboxylate having at least one phenyl group and at least one functional group X attached to at least one phenyl group.
  • the IRMOF formed has a substantially permanent porosity and is very stable, with or without the presence of guest molecules.
  • M in the SBU is a metal cation of a metal selected from the group consisting of beryllium, zinc, cadmium, mercury, and any of the transition metals (in the periodic table, scandium through copper, yttrium through silver, lanthanum through gold, and all known elements from actinium on).
  • X may be any suitable functional group as necessary and/or desired. In the preferred embodiment, X is selected from the group enumerated hereinabove.
  • a method of forming an isoreticular metal-organic framework comprises the step of dissolving at least one metal salt and at least one linear ditopic carboxylate in a solvent to form a solution.
  • the solvent may be any suitable solvent, however, in the preferred embodiment, the solvent is any nitrogen containing solvent having a boiling point of less than about 250°C. The solution is then crystallized to form the targeted IRMOF.
  • the metal salt is formed from a metal cation and an anion, the metal cation being a cation of a metal selected from the group consisting of beryllium, zinc, cadmium, mercury, and any of the transition metals.
  • the anion is selected from the group consisting of F - , Cl - , Br - , I - , ClO - , ClO 2 - , ClO 3 - , ClO 4 - , OH - , NO 3 - , NO 2 - , SO 4 2- , SO 3 2- , PO 4 3- , CO 3 2- , and PF 6 - and organic counter ions such as acetate CH 3 CO 2 2- , triphlates CF 3 SO 3 - .
  • the linear ditopic carboxylate/carboxylic acid has at least one phenyl group.
  • at least one functional group X is attached to the at least one phenyl group. X is as defined hereinabove.
  • the crystallizing step is carried out by: leaving the solution at room temperature; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and/or transferring the solution to a closed vessel and heating to a predetermined temperature.
  • the method of the present invention has advantageously formed very high yields (about 93%) of pure IRMOF either without any base at all, or by addition (not diffusion) of base into the solution.
  • the linking compounds/ligands possessing multi- and/or poly-dentate functional groups may or may not bring with them one or more corresponding counter cations, such as, for example, H + , Li + , Na + , K + , Mg 2+ , Ca 2+ , Sr 2+ , ammonium ion, alkylsubstituted ammonium ions, and arylsubstituted ammonium ions, or one or more counter anions, such as, for example, F - , Cl - , Br - , I - , ClO - , ClO 2 - , ClO 3 - , ClO 4 - , OH - , NO 3 - , NO 2 - , SO 4 2- , SO 3 2- , PO 4 3- , CO 3 2- , and PF 6 - and organic counter ions such as acetate CH 3 CO 2 2- , triphlates CF 3 SO 3 - .
  • counter cations such
  • the crystalline microporous materials of the present invention may be synthesized using metal ions having distinctly different coordination geometries, in combination with a ligand possessing multi- and/or poly-dentate functional groups.
  • the metal ions may be in the form of a metal salt formed from the metal ions with anions, such as, for example, F - , Cl - , Br - , I - , ClO - , ClO 2 - , ClO 3 - , ClO 4 - , OH - , HCO 2 - , NO 3 - , NO 2 - , SO 4 2- , SO 3 2- , PO 4 3- , CO 3 2- , B 4 O 7 2- and PF 6 - and organic counter ions such as acetate CH 3 CO 2 2- , triphlates CF 3 SO 3 - .
  • anions such as, for example, F - , Cl - , Br - , I - , ClO - , ClO 2 - , ClO 3 - , ClO 4 - , OH - , HCO 2 - , NO 3 - , NO 2 - , SO 4 2- , SO 3 2-
  • the yellow spheres represent the largest van der Waals spheres that would fit in the cavities without touching the frameworks.
  • IRMOF-2-16 including the non-interpenetrating structures of BPDC, HPDC, PDC, and TPDC.
  • the solvent used to synthesize the IRMOFs be N,N'-diethylformamide (DEF) or combined with other solvents such as alcohols and the like.
  • IRMOFs may also be made using any formamide derivatives, eg. N, N'-R 2 formamide (R may be an alkane, alkene, and the like) as a predominant solvent or mixed.
  • IRMOFs have the expected topology of CaB 6 (see M. O'Keeffe and B.G. Hyde, Crystal Structures I : Patterns and Symmetry (Mineralogy Society of America, Washington, DC, 1996)) adapted by the prototype IRMOF-1 (Fig. 37), in which an oxide-centered Zn 4 O tetrahedron is edge-bridged by six carboxylates to give the octahedron-shaped SBU that reticulates into a 3-D cubic porous network.
  • the IRMOFs differ in the nature of functional groups decorating the pores and in the metrics of their pore structure.
  • the present invention shows that expansion of the pores is also contemplated as being within the purview of the present invention. This is illustrated by the structures of IRMOF-8 to 16 (Figs. 8 to 16), in which progressively longer links have been successfully employed.
  • methane constitutes one of the most abundant sources of energy on earth, it is the least utilized source of fuel due to the long-standing challenge in its transport and storage at practical temperatures and pressures; conditions believed to be attainable by sorption of methane into porous materials. See V.C. Menon, S. Komaeneni, J. Porous Mater. 5 , 43 (1998).
  • IRMOF-6 has an aperture (van der Waals dimension of 5.9 ⁇ ) (Van der Waals radius of C (1.70 ⁇ ) was employed in determination of distance parameters; Bondi, A. J. Phys. Chem. 68 , 441 (1964)) considered to be suitable for methane uptake, the present inventors sought to examine its viability in methane storage.
  • the gas sorption isotherm was measured for IRMOF-6 to show that it has a rigid framework, and that it can maintain its porosity in the absence of guests.
  • An exact amount of the chloroform-exchanged IRMOF-6 was introduced into a microbalance apparatus, and evacuated at room temperature and 10-5 torr according to already published protocol. See M. Eddaoudi, H. Li and O.M. Yaghi, J. Am. Chem. Soc. 122 , 1391 (2000). All the chloroform guest molecules were removed from the pores, as confirmed by the fact that no additional weight change was observed upon evacuating the sample overnight and heating it to 150°C.
  • the evacuated sample was also exposed to different organic vapors (CH 2 Cl 2 , C 6 H 6 , CCl 4 and C 6 H 12 ) to also give type I reversible isotherms (Fig. 55B), and pore volumes that converged to the same values (0.57 to 0.60 cm 3 /cm 3 ) for all sorbents, further confirmation of the homogeneity of the pores. See S.J. Gregg and K.S.W., Adsorption Surface Area and Porosity , Academic Press, London, UK, 2nd Ed (1982).
  • the amount of methane sorbed by IRMOF-6 at 36 atm (generally regarded as a substantially safe and cost effective pressure limit), represents 70% of the amount generally stored in laboratory compressed methane cylinders in which significantly higher, less cost effective, and (in certain circumstances) potentially less safe pressure (205 atm) is employed. It is believed that the present invention is an advance which will impact the impending use of these materials in automobile fueling. See U.S. Patent No. 5,862,796, issued to K. Seki et al. on January 26, 1999.
  • Methane uptake was also evaluated by testing IRMOF-1 and IRMOF-2 under the same conditions where their uptake was found to be lower (135 and 120 cm 3 /cm 3 ) than that of IRMOF-6--a significant difference that may be attributable to the hydrophobic nature of H 4 C 2 units in IRMOF-6.
  • IRMOF-1 and IRMOF-2 under the same conditions where their uptake was found to be lower (135 and 120 cm 3 /cm 3 ) than that of IRMOF-6--a significant difference that may be attributable to the hydrophobic nature of H 4 C 2 units in IRMOF-6.
  • functionalizing the pores with larger hydrocarbons as illustrated in IRMOF-4, 5, and 7, may indeed result in even higher capacities.
  • the present invention provides a unique approach that succeeds in the assembly of pre-designed rigid skeletal backbone structure and in imparting functionality and metric variation onto its pores, ultimately leading to functional materials capable of high uptake of gases and organic vapors.
  • the intrinsic value of this design approach lies in the ability to control and direct the outcome of molecular assembly of extended networks. It is believed that the present invention ushers a new era in solid-state synthesis.
  • Method 1 1,4-benzenedicarboxylic acid, H 2 BDC, (0.070 g, 0.42 mmol) and zinc nitrate hexahydrate, Zn(NO 3 ) 2 •6H 2 O, (0.250 g, 0.84 mmol) were dissolved in 10mL dimethylformamide, DMF. Then, 0.10 ml of hydrogen peroxide, H 2 O 2 , (30% aqueous) was added, followed by the addition of 0.10 mL of 50 times diluted dimethylamine (DMA) (40% aqueous) in DMF. The resultant mixture was diluted again 10 times with DMF. After several days ( ⁇ 7-10 days), a pure phase IRMOF-1 was formed.
  • DMA dimethylamine
  • the ZnO 4 tetrahedra are indicated in purple.
  • the frameworks interconnect to form a 3-D stable, porous crystalline structure.
  • Method 2 1,4-benzenedicarboxylic acid, H 2 BDC, (0.033 g, 0.20 mmol) and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 •4H 2 O, (0.156 g, 0.60 mmol) were dissolved in 5 ml diethylformamide (DEF) and left at room temperature. After one week, the desired compound IRMOF-1 was formed in high yield ( ⁇ 85%). The purity of the as-synthesized compound was confirmed by X-ray powder diffraction (XRPD) pattern as shown in Figure 2b.
  • XRPD X-ray powder diffraction
  • Method 3 An exact amount of 1,4-benzenedicarboxylic acid, H 2 BDC, (0.033 g, 0.20 mmol) and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 •4H 2 O, (0.156 g, 0.60 mmol) was dissolved in 5 ml diethylformamide, DEF, and placed in a Parr Teflon-lined stainless steel vessel (23 mL). The vessel was sealed and heated at a constant rate 2°C/min to 105°C for 20 h and then cooled to room temperature at a rate of 1°C/min. The resultant compound was a pure IRMOF-1 as confirmed by X-ray powder diffraction (XRPD) pattern as shown in Figure 2c .
  • XRPD X-ray powder diffraction
  • FT-IR (KBr, 3500-400 cm -1 ): 3455 (br), 2982 (m), 2940 (w), 2874(w), 1668 (vs), 1647 (s), 1622 (s), 1556(w), 1485(m), 1449 (s), 1387 (vs), 1260 (m), 1214 (m), 1118 (w), 1042 (w), 827 (w), 776 (w), 741 (w), 665 (w), 542(w).
  • Zn 4 O(H 2 NBDC) 3 •(DEF) x (IRMOF-3): A mixture of diethylformamide and ethanol DEF/C 2 H 5 OH : 9/3 ml containing 2-amino 1,4 benzenedicarboxylic acid, H 2 BDCNH 2 , (0.036 g, 0.20 mmol) and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 •4H 2 O, (0.156 g, 0.60 mmol) was placed in a Parr Teflon-lined stainless steel vessel (23 mL).
  • the vessel was sealed and heated at a constant rate 2°C/min to 105°C for 20 h and then cooled to room temperature at a constant rate of 1° C/min.
  • the resultant product, IRMOF-3 (90%) was filtered and washed with DEF/ethanol mixture (3 x 5mL).
  • IRMOF-3 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • Infra-Red spectra for IRMOF-3 ( Figure 5 ): FT-IR for IRMOF-3 (KBr, 3500-400 cm -1 ): Infrared spectra characteristic peaks 3455 (br), 3338 (br), 2976 (m), 2936 (w), 2879 (w), 1673 (vs), 1571 (s), 1495 (w), 1433 (s), 1387 (vs), 1260 (m), 1214 (m), 1153 (w), 1113 (w), 944 (w), 899 (w), 827 (w), 782 (m), 710 (w), 717 (m), 644 (w), 593 (w), 517 (w).
  • the nitrogen sorption at 78K was monitored by introducing different increments of nitrogen gas to the sample chamber.
  • the nitrogen sorption isotherm is a Type I isotherm and fully reversible, characteristic of a microporous material ( ⁇ 2.0 nm).
  • the plateau was reached at relatively low pressure with no additional uptake at relatively medium pressures (near condensation pressure P/P 0 ⁇ 0.5), confirming the homogeneity of the pores and the absence of any mesorporosity or macroporosity.
  • the evacuated sample was also exposed to different organic vapors such as dichloromethane CH 2 Cl 2 , benzene C 6 H 6 , carbon tetrachloride CCl 4 and cyclohexane C 6 H 12 . All the resultant isotherms were Type I and reversible as shown in Figure 10 .
  • Table 1 The data are summarized in Table 1 , and they indicate that, regardless of the sorbed guest, the pore volumes converge to the same values (0.52-0.59 cm 3 /cm 3 ): final proof of the homogeneity of the pores.
  • the resultant cubic IRMOF-3 crystals were collected and fully characterized.
  • the crystallographic parameters and a picture of the framework are summarized in Figure 3.
  • the elemental analysis confirms the composition as discussed above, and the Infrared spectrum confirms that the carboxylates are fully deprotenated.
  • the overlap of the observed and simulated XRPD confirms the purity of the sample.
  • Diethylformamide molecules occupied the void spaces in the porous structure of IRMOF-3.
  • the DEF guest molecules can be removed from the pores under extended vacuum or by heating the sample as shown in Figure 6.
  • the DEF guest molecules can also be fully exchanged with a volatile molecule, such as chloroform, as proven by the data above.
  • IRMOF-3 maintains its structure and mainly its porosity upon removing the guest molecules
  • sorption studies were carried out on the fully evacuated IRMOF-3.
  • the isotherm is a type I isotherm characteristic of a microporous material (Nitrogen sorption isotherm is a universal and powerful tool to characterize porous material).
  • the data summarized in Table 1 prove that IRMOF-3 has homogeneous porosity and is able to sorb different guest molecules. It is believed that the stability of the framework may primarily be due to the stability of the M 4 O(CO 2 ) 6 cluster (secondary building unit).
  • FT-IR (KBr, 3500-400 cm -1 ): 3455 (br), 2976 (m), 2941 (w), 2936 (w), 2879 (w), 1663 (s), 1607 (vs), 1495 (w), 1423 (vs), 1494 (w), 1393 (s), 1270 (m), 1210 (m), 1118 (w), 1067 (w), 980 (w), 802 (m), 746 (w), 644 (w), 552 (w).
  • FT-IR (KBr, 3500-400 cm -1 ): 3445 (br), 2961 (m), 2931 (m), 2865 (w), 1658(s), 1607 (vs), 1495 (w), 1429 (vs), 1388 (s), 1281 (w), 1200 (m), 1052 (w), 1006 (w), 904 (w), 807 (m), 761 (w), 731 (w), 665 (w), 552 (w).
  • Zn 4 O([C 2 H 4 ]BDC) 3 •(DEF) x (IRMOF-6): cyclobutene 1,4-benzenedicarboxylic acid, H 2 BDC[C 2 H 4 ], (0.045 g, 0.20 mmol) and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 •4H 2 O, (0.156 g, 0.60 mmol) were dissolved in 12mL diethylformamide, DEF and placed in a Parr Teflon-lined stainless steel vessel (23 mL). The vessel was sealed and heated at a constant rate (2°C/min) to 105°C for 20 h and then cooled to room temperature at a rate of 1° C/min.
  • the resultant sample (92%), IRMOF-2, was filtered and washed with DEF (3 x 5mL). It is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • Phase purity of the bulk product was confirmed by comparison of the observed X-ray powder diffraction (XRPD) pattern, shown in Figure 12a, and the calculated X-ray powder diffraction pattern, shown in Figure 12b, simulated from the single-crystal structure data of IRMOF-2, Zn 4 O([C 2 H 4 ]BDC) 3 •(DEF) x .
  • XRPD X-ray powder diffraction
  • Infra-Red spectra for IRMOF-6 ( Figure 13): FT-IR for IRMOF-6 (KBr, 3500-400 cm -1 ): 3419 (br), 2976 (m), 2936 (m), 2365 (w), 2340 (w), 1668 (s), 1605 (vs), 1489 (m), 1398 (vs), 1303 (w), 1265 (w), 1112 (w), 941 (w), 812 (m), 782 (m), 735 (w), 542 (m).
  • the nitrogen sorption at 78K was monitored by introducing different increments of nitrogen gas to the sample chamber.
  • the sorption isotherm is a Type I isotherm and fully reversible, characteristic of a microporous material ( ⁇ 2.0nm).
  • the plateau was reached at relatively low pressure with no additional uptake at relatively medium pressures (near condensation pressure P/P 0 ⁇ 0.5), confirming the homogeneity of the pores, and the absence of mesorpores and macropores.
  • the evacuated sample was also exposed to different organic vapors (CH 2 Cl 2 , C 6 H 6 , CCl 4 and C 6 H 12 ) and all the isotherms were Type I and reversible.
  • the data are summarized in Table 2, and they show that the pore volume converge to the same values (0.57-0.60 cm 3 /cm 3 ), proving the homogeneity of the pores.
  • the resultant IRMOF-6 cubic crystals were collected and fully characterized.
  • the crystallographic parameters and a representative picture of the framework are summarized in Figure 11.
  • the elemental analysis confirms the composition as shown above, the Infrared confirms that the carboxylates are fully deprotenated.
  • the overlap of the observed and simulated XRPD confirms the purity of the sample.
  • Diethylformamide molecules occupied the void spaces in the porous structure of IRMOF-6.
  • the DEF guest molecules can be removed from the pores under extended vacuum or by heating the sample as shown in Figure 14.
  • the DEF guest molecules can also be fully exchanged with a volatile, molecule such as chloroform as proven by the data above.
  • IRMOF-6 maintains its structure and mainly its porosity upon removing the guest molecules sorption studies were carried out on the fully evacuated IRMOF-6.
  • the isotherm is a type I isotherm characteristic of a microporous material.
  • Table 2 prove that IRMOF-6 has homogeneous porous and able to sorb different guests molecules.
  • Zn 4 O(2,4NDC) 3 •(DEF) x (IRMOF-7): An exact amount of 2,4 naphthalene dicarboxylic acid, (2,4 H2NDC) (0.015 g, 0.072 mmol), and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 •4H 2 O, (0.0.53 g, 0.20 mmol), were dissolved in 5mL diethylformamide, DEF, and placed in a Parr Teflon-lined stainless steel vessel (23 mL). The vessel was sealed and heated at a constant rate (2°C/min) to 85°C for 20 h and then cooled to room temperature at a rate of 1 ° C/min.
  • IRMOF-7 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • the observed X-ray powder diffraction pattern shown in Figure 19a was compared to the simulated one in Figure 19b to confirm the purity of the as-synthesized IRMOF-7, Zn 4 O(2,4NDC) 3 •(DEF) x .
  • FT-IR (KBr, 3500-400 cm -1 ): 3435 (br), 2980 (w), 2935 (w), 2340 (w), 1644 (s), 1605 (vs), 1519 (m), 1466 (m), 1413 (s), 1361 (vs), 1263 (m), 1220 (w), 1163 (w), 1108 (w), 840 (w), 792 (w), 562 (w).
  • IRMOF-8 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • the observed X-ray powder diffraction pattern is shown in Figure 20 .
  • FT-IR (KBr, 4000-400 cm -1 ): 3430 (br), 2981 (w), 2935 (w), 2870 (w), 1663 (vs), 1607 (vs), 1545 (m), 1403 (vs), 1347 (s), 1311 (w), 1265 (w), 1220 (w), 1184 (w), 1113 (w), 1011 (w), 777 (m), 705 (w), 680 (w), 644 (w), 456 (w).
  • Method 2 A mixture of N,N' dimethylformamide and benzene DMF/2-C 3 H 8 OH : 4/4 ml containing 4, 4' biphenyl dicarboxylic acid, H 2 BPDC, (0.015 g, 0.062 mmol) and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 ⁇ 4H 2 O, (0.130 g, 0.50 mmol) was placed in a Parr Teflon-lined stainless vessel (23 mL). The vessel was sealed and heated to 85 °C for 24 h at a rate of 2.0 °C/min and cooled to room temperature at a rate of 2.0 °C/min.
  • IRMOF-9 The as-synthesized IRMOF-9 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • the observed X-ray powder diffraction pattern is shown in Figure 22a, and the simulated pattern from the single X-Ray data is shown in Figure 22b.
  • the vessel was sealed and heated to 85 °C for 24 h at a rate of 2.0 °C/min and cooled to room temperature at a rate of 2.0 °C/min.
  • the resultant product was filtered, washed with a DMF/benzene mixture (3 x 5mL) to give 60% of IRMOF-9.
  • the as-synthesized IRMOF-9 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • the observed X-ray powder diffraction pattern is shown in Figure 22a
  • the simulated pattern from the single X-Ray data is shown in Figure 22b .
  • FT-IR for IRMOF-9 FT-IR (KBr, 4000-400 cm-1): 3430 (br), 2936 (w), 1658 (m), 1612 (s), 1541 (w), 1505 (w), 1403 (vs), 1261 (w), 1184 (w), 1108 (w), 1016 (w), 863 (w), 848 (w), 802 (w), 772 (m), 711 (w), 685 (w), 588 (br), 461 (w).
  • FT-IR (KBr, 3500-400 cm -1 ): 3455 (br), 2981 (m), 2941 (w), 2880 (w), 1668 (vs), 1607 (vs), 1546 (m), 1398 (s), 1311 (w), 1265 (m), 1220 (m), 1118 (w), 1011 (w), 950 (w), 827 (w), 777 (m), 690 (w), 556 (w).
  • FT-IR (KBr, 4000-400 cm -1 ): 3430 (br), 2977 (w), 2941 (w), 2890 (w), 2840 (w), 1647 (vs), 1601 (s), 1548 (m), 1464 (m), 1398 (vs), 1352 (s), 1301 (w), 1270 (w), 1245 (w), 1214 (w), 1113 (w), 1091 (w), 1006 (w), 827 (w), 650 (w).
  • Method 2 Zn 4 O(TPDC) 3 •4H 2 O•9DMF (IRMOF-11): A mixture of dimethylformamide and isopropanol DMF/2-C 3 H 8 OH : 6/2 ml containing tetrahydropyrene-2,7-dicarboxylic acid, H 2 TPDC (0.015 g, 0.051 mmol), and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 •4H 2 O (0.080 g, 0.31 mmol), was placed in a Parr Teflon-lined stainless vessel (23 mL).
  • the vessel was sealed and heated to 85 °C for 24 h at a rate of 2.0 °C/min and cooled to room temperature at a rate of 2.0 °C/min.
  • the resultant product rectangular, pale yellow crystals, was filtered, washed with a DMF and isopropanol mixture (3 x 5mL) to yield 69% of IRMOF-11.
  • the as-synthesized IRMOF-11 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • Thermogravimetric analysis for IRMOF-11 A crystalline sample (16.527 mg) was heated from 30 °C to 900 °C at 5.0 °C/min; two separate weight-loss steps were observed. The first weight loss (38.1 %) step at 250 °C corresponds to the removal of (4H 2 O + 9DMF) and the second, which occurs above 400 °C (41.8 %), corresponds to framework decomposition. A plateau between 250 - 400 °C was observed, confirming the stability of the evacuated framework IRMOF-11 up to 400 °C.
  • the resultant IRMOF-11 cubic crystals were collected and fully characterized.
  • the crystallographic parameters and a representative picture of the framework are summarized in Figure 27 .
  • the elemental analysis confirms the composition as shown above, the Infrared confirms that the carboxylates are fully deprotenated.
  • the overlap of the observed and simulated XRPD confirms the purity of the sample.
  • FT-IR (KBr, 3500-400 cm -1 ): 3455 (br), 2982 (m), 2941 (m), 2879 (w), 1668 (vs), 1602 (s), 1551 (m), 1464 (m), 1434 (m), 1393 (vs), 1352 (m), 1306 (w), 1266 (w), 1220 (w), 1113 (w), 920 (w), 827 (w), 797 (m), 761 (m), 650(w).
  • the as-synthesized IRMOF-12 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • the observed X-ray powder diffraction pattern is shown in Figure 25a, and the pattern simulated from the single X-Ray data is shown in Figure 25b . Comparison of these two patterns confirms the purity of the as-synthesized IRMOF-12.
  • Infra-Red spectra for IRMOF-12 ( Figure 26 ): FT-IR for IRMOF-12 FT-IR (KBr, 4000-400 cm -1 ): 3434 (br), 3063 (w), 2931 (w), 2890 (w), 2829 (w), 1800 (w), 1581 (s), 1530 (s), 1464 (m), 1429 (s), 1393 (vs), 1352 (s), 1245 (w), 1128 (w), 1082 (w), 1026 (w), 1006 (w), 909 (w), 792 (w), 741 (w), 706 (w), 685 (w), 471 (w).
  • Thermogravimetric analysis of IRMOF-12 A crystalline sample (16.527 mg) was heated from 30 °C to 900 °C at constant rate (5.0 °C/min); two separate weight-loss steps were observed. The first weight loss step (38.1 %) at 250 °C corresponds to the removal of (4H 2 O + 9DMF) and the second one (41.8 %) to the decomposition of the framework. A pseudo-plateau was observed between 250°C - 400°C corresponding to the stability of IRMOF-6 up to 400 °C.
  • the resultant IRMOF-12 crystals were fully characterized as discussed above.
  • the crystallographic parameters and a representative picture of the framework are summarized in Figure 24 .
  • the elemental analysis confirms the composition as shown above, the Infrared confirms that the carboxylates are fully deprotonated.
  • the overlap of the observed and simulated XRPD confirms the purity of the sample.
  • Zn 4 O(PDC) 3 • 4H 2 O• 6DEF (IRMOF-13): Exact amounts of ppyrene-2,7- dicarboxylic acid, H 2 TPDC (0.014g, 0.048 mmol), and zinc nitrate hexahydrate, Zn(NO 3 ) 2 •4H 2 O (0.080 g, 0.31 mmol), were dissolved in diethylformamide, DEF, (6.0 mL) and placed in a Parr Teflon-lined stainless vessel (23 mL). The vessel was sealed and heated to 85 °C for 24 h at a rate of 2.0 °C/min and cooled to room temperature at a rate of 2.0 °C/min.
  • IRMOF-13 The as-synthesized IRMOF-13 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • XRPD X-ray powder diffraction
  • Infra-Red spectra for IRMOF-13 ( Figure 34): FT-IR for IRMOF-13 (KBr, 4000-400 cm -1 ): 3445 (br), 2977 (w), 2936 (w), 2880 (w), 1648 (s), 1612 (s), 1581 (s), 1464 (s), 1393 (vs), 1312 (w), 1261 (m), 1209 (w), 1108 (w), 914 (w), 823 (w), 777 (w), 746 (w), 711 (w), 670 (w), 553 (w).
  • Thermogravimetric analysis for IRMOF-13 A crystalline sample (22.256mg) was heated from 25 °C to 700 °C at a constant rate (5.0 °C/min); two separate weight-loss steps were observed. The first weight loss (31.4 %) step below 300 °C corresponds to the removal of (4H 2 O + 6DEF) and the second one above 420 °C (42.7 %) to the framework decomposition. A pseudo-plateau between 300 - 420 °C was observed, proving the stability of IRMOF-13.
  • Method 1 Exact amounts of pyrene-2,7- dicarboxylic acid, H 2 PDC (0.005g, 0.017 mmol), and zinc nitrate hexahydrate, Zn(NO 3 ) 2 ⁇ 4H 2 O (0.031 g, 0.12 mmol), were dissolved in diethylformamide, 16ml, DEF and placed in a Parr Teflon-lined stainless vessel (23 mL). The vessel was sealed and heated to 85 °C for 24 h at a rate of 2.0°C/min and cooled to room temperature at a rate of 2.0 °C/min. The resultant product was filtered, washed with a DEF (3 x 5mL) to yield 70% of IRMOF-14.
  • FT-IR (KBr, 3500-400 cm -1 ): 3455 (br), 2982 (m), 2935 (w), 1658 (s), 1607 (s), 1581 (m), 1464 (m), 1393 (s), 1261 (m), 1220 (w), 1113 (w), 914 (w), 827 (m), 751 (w), 711 (w), 511 (w).
  • Method 2 Zn 4 O(PDC) 3 ⁇ 4H 2 O ⁇ 1/2CHP ⁇ 10chlorobenzne (IRMOF-14): A mixture of dimethylformamide and isopropanol DMF/2-C 3 H 8 OH : 6/1ml containing pyrene-dicarboxylic acid, H 2 PDC (0.014 g, 0.048 mmol), and zinc nitrate tetrahydrate, Zn(NO 3 ) 2 ⁇ 4H 2 O (0.080 g, 0.31 mmol), was placed in a Parr Teflon-lined stainless vessel (23 mL).
  • the vessel was sealed and heated to 85 °C for 24 h at a rate of 2.0 °C/min and cooled to room temperature at a rate of 2.0 °C/min.
  • the filtrate solution from six vessels (35 mL) was diluted with CHP (1-cyclohexyl-2-pyrrolidinone) (15.0 mL).
  • the final solution was divided equally, transferred into five vials, and exposed to diluted triethylamine.
  • IRMOF-14 was filtered, washed with a DMF and chlorobenzene mixture (3 x 5mL) to yield 6% of IRMOF-14.
  • the as-synthesized IRMOF-14 is insoluble in water and all common organic solvents such as ethanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, acetone, N,N'-dimethylformamide, and N,N'-diethylformamide.
  • Figure 31a Comparison of the observed X-ray powder diffraction pattern shown in Figure 31a and the simulated pattern from the single X-Ray data ( Figure 31b) confirms the purity of the as-synthesized IRMOF-14.
  • Infra-Red spectra for IRMOF-14 ( Figure 32 ): FT-IR for IRMOF-14 FT-IR (KBr, 4000-400 cm -1 ): 3430 (br), 3048 (w), 2936 (w), 2854 (w), 1607 (m), 1571 (m), 1464 (m), 1393 (vs), 1317 (w), 1261 (m), 1087 (w), 909 (w), 823 (w), 746 (m), 706 (w), 685 (w), 471 (w).
  • Thermogravimetric analysis of IRMOF-14 A crystalline sample (12.000 mg) was heated from 30 °C to 800°C at 10.0 °C/min; two separate weight-loss steps were observed. The first weight loss (52.4 %) step at 250 °C is attributed to the removal of (4H 2 O + 1/2CHP + 10chlorobenzne) and the second one (34.9 %) to the framework decomposition. A pseudo plateau was observed between 250 - 300 °C indicating the stability of IRMOF-14 up to 300°C.
  • the resultant IRMOF-14 crystals after two weeks, were collected and fully characterized.
  • the crystallographic parameters and a representative picture of the framework are summarized in Figure 30 .
  • the elemental analysis confirms the composition as shown above, the Infrared confirms that the carboxylates are fully deprotenated.
  • the overlap of the observed and simulated XRPD confirms the purity of the sample.
  • Infra-Red spectra for IRMOF-15 ( Figure 36): FT-IR for IRMOF-15 (KBr, 4000-400 cm -1 ): 3451 (br), 2978 (w), 2939 (w), 2877 (w), 1667 (s), 1607 (s), 1545 (w), 1404 (vs), 1393 (vs), 1114 (w), 780 (w).
  • IRMOF-15 clear cubic crystals were collected and characterized.

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Claims (16)

  1. Ein systematisch angeordnetes isoretikuläres metallorganisches Framework (Rahmenwerk) (IRMOF), enthaltend:
    eine Vielzahl von sekundären Baueinheiten (SBUs), jede dieser Vielzahl von SBUs enthält ein M4O(CO2)6 Cluster; und
    eine Verbindung verbindend benachbarte SBUs, die verbindende Verbindung enthält ein lineares ditopisches Carboxylat, aufweisend mindestens eine substituierte Phenylgruppe und mindestens eine funktionale Gruppe X verbunden mit der mindestens einen substituierten Phenylgruppe;
    wobei das IRMOF eine im Wesentlichen permanente Porosität hat und im Wesentlichen stabil ist;
    wobei die funktionale Gruppe X mindestens eine ist aus Wasserstoff, Aminen, Halogeniden, eine R-Gruppe ausgewählt aus mindestens einer linearen, substituierten oder Cyklo- Alkane, Alkene, Alkine, Ketten und Ether O-R, wobei R mindestens eine lineare, substituierte oder Cyklo- Alkane, Alkene, Alkine, Ketten, und Mischungen davon;
    und wobei mindestens eine Funktion, Dimension und Porengröße und freies Volumen des IRMOF im Wesentlichen durch die verbindende Verbindung bestimmt ist und wobei die verbindende Verbindungen die Gruppe umfasst ausgewählt aus:
    Figure imgb0010
    Figure imgb0011
    Figure imgb0012
  2. Der IRMOF, wie definiert in Anspruch 1, wobei X umfasst mindestens ein primäres, sekundäres oder tertiäres Amin; aromatisches Amin, Pyridin, Pyrimidin, wie 5 oder 6 gliedrige Ringe; Halogenide, beinhaltend substituierte -RX; Alkohole: ROH; Thiole: RSH; Sulfonate -R-SO3; Nitrogruppen -R(NO2); Phosphate -R-PO2 -; Epoxide; Aldehyde (RCOH); Ketone (RCOR); Ester RCO2R; Carbonsäuren; Cycloalkene, Cykloalkine, Silylderivate; Boranderivate, Ferrocene, andere Metallocene, und Mischungen davon.
  3. Der IRMOF, wie definiert in Anspruch 1, wobei M in der SBU ein Metallkation ist aus mindestens einem Metall ausgewählt aus Beryllium, Zink, Cadmium, Quecksilber, eines der Übergangsmetalle im Periodensystem, Scandium bis Kupfer, Yttrium bis Silber, Lanthanium bis Gold und alle bekannten Elemente von Actinium an.
  4. Ein Verfahren zur systematischen Anordnung eines isoretikulären metallorganischen Framework (Rahmenwerk) (IRMOF), das Verfahren umfasst die Schritte:
    Lösen mindestens eines Metallsalzes und mindestens einer organischen verbindenden Verbindung in einem Lösungsmittel zur Bildung einer Lösung unter vorgegebenen Bedingungen zum Herstellen von M4O(CO2)6 in situ; die mindestens eine organische verbindende Verbindung enthält ein lineares ditopisches Carboxylat mit mindestens einer substituierten Phenylgruppe und mindestens einer funktionalen Gruppe X verbunden mit der mindestens einen substituierten Phenylgruppe, wobei die verbindenden Verbindungen ausgewählt sind aus Gruppe gemäß Anspruch 1; und
    Kristallisieren der Lösung unter vorgegebenen Bedingungen zur Bildung eines IRMOF;
    wobei mindestens eine in Funktionalität, Dimension, Porengröße und freies Volumen des IRMOF im Wesentlichen durch die organische verbindende Verbindung bestimmt ist.
  5. Das Verfahren, wie definiert in Anspruch 4, wobei mindestens ein Metallsalz aus einem Metallkation und einem Anion gebildet ist; das Metallkation ist ein Kation aus einem Metall ausgewählt aus der Gruppe bestehend aus Zink, Cadmium, Quecksilber und Übergangsmetalle und wobei das Anion ausgewählt ist aus der Gruppe bestehend aus F-, Cl-, Br-, I-, ClO-, ClO2 -, ClO3 -, ClO4 - , OH-, NO3 -, NO2 - , SO4 2-, SO3 2-, PO4 3-, CO3 2-, CH3CO2 -, HCO2 - und CF3SO3 -, B4O7 2- und PF6 -.
  6. Das Verfahren, wie definiert in Anspruch 4, wobei die vorgegebenen Bedingungen sind mindestens eine von:
    Belassen der Lösung bei Raumtemperaturen; Zufügen einer gelösten Base zu der Lösung zur Initiierung der Kristallisation; Diffundieren einer gelösten Base in die Lösung zur Initiierung der Kristallisation; und
    Überführen der Lösung in ein geschlossenes Gefäß und Heizen bei vorgegebener Temperatur.
  7. Ein systematisch angeordnetes isoretikuläres metallorganisches Framework (Rahmenwerk) (IRMOF) enthaltend:
    eine Vielzahl von sekundären Baueinheiten (SBUs), jede der Vielzahl von SBUs enthält ein M4O(CO2)6 Cluster; und
    eine Verbindung verbindend benachbarte SBU, die verbindende Verbindung enthält ein lineares ditopisches Carboxylat, aufweisend mindestens eine substituierte Phenylgruppe und mindestens eine funktionale Gruppe X verbunden mit der mindestens einen substituierten Phenylgruppe, wobei die verbindenden Verbindungen ausgewählt sind aus der Gruppe gemäß Anspruch 1;
    wobei der IRMOF eine im Wesentlichen permanente Porosität hat und im Wesentlichen stabil ist;
    wobei mindestens eine in Funktionalität, Dimension und Porengröße und freies Volumen des IRMOF im Wesentlichen durch die verbindende Verbindung bestimmt ist;
    und wobei der IRMOF zum Speichern mindestens eines Gases angepasst ist.
  8. Ein systematisch angeordnetes isoretikuläres metallorganisches Framework (Rahmenwerk) (IRMOF) enthaltend:
    eine Vielzahl von sekundären Baueinheiten (SBUs), jede dieser Vielzahl von SBUs enthält ein M4O(CO2)6 Cluster; und
    eine Verbindung verbindend benachbarte SBUs, die verbindende Verbindung enthält ein lineares ditopisches Carboxylat, aufweisend zumindest eine substituierte Phenylgruppe und mindestens eine funktionale Gruppe X verbunden mit der mindestens einen substituierten Phenylgruppe; wobei die verbindenden Verbindungen ausgewählt sind aus der Gruppe gemäß Anspruch 1;
    wobei der IRMOF eine im Wesentlichen permanente Porosität hat und im Wesentlichen stabil ist;
    wobei mindestens eine in Funktionalität, Dimension, Porengröße und freies Volumen des IRMOF im Wesentlichen durch die verbindende Verbindung bestimmt ist;
    und wobei der IRMOF zum Speichern von Methan angepasst ist.
  9. Der IRMOF, wie definiert in Anspruch 1, wobei die Dichte des IRMOF ungefähr zwischen 1,0 g/cm3 und ungefähr 0,2 g/cm3 ist.
  10. Der IRMOF, wie definiert in Anspruch 9, wobei die Dichte des IRMOF zwischen ungefähr 0,41 g/cm3 und ungefähr 0,21 g/cm3 ist.
  11. Der IRMOF, wie definiert in Anspruch 9, wobei die Methan Speicherungskapazität ungefähr 155 cm3/cm3 ist.
  12. Das Verfahren, wie definiert in Anspruch 4, wobei der IRMOF eine Vielzahl von sekundären Baueinheiten (SBUs) ist.
  13. Das Verfahren, wie definiert in Anspruch 12, wobei jedes der SBUs ein Multimetall-Kern-Carboxylat-Cluster ist.
  14. Das Verfahren, wie definiert in Anspruch 13, wobei der Multimetall-Kern-Carboxylat-Cluster M4O(CO2)6 ist.
  15. Ein Verfahren zum systematischen Anordnen eines isoretikulären metallorganischen Framework (Regelwerk) (IRMOF), das Verfahren umfasst die Schritte:
    Lösen mindestens eines Metallsalzes und mindestens einer organischen verbindenden Verbindung in einem Lösungsmittel zur Bildung einer Lösung; und
    Kristallisieren der Lösung unter vorgegebenen Bedingungen zur Bildung eines IRMOF;
    wobei mindestens eine in Funktionalität, Dimension, Porengröße und freies Volumen des IRMOF im Wesentlichen durch die organische verbindende Verbindung bestimmt ist,
    wobei mindestens ein Metallsalz aus einem Metallkation und einem Anion gebildet ist; das Metallkation ist ein Kation aus einem Metall ausgewählt aus der Gruppe bestehend aus Zink, Cadmium, Quecksilber und Übergangsmetalle und wobei das Anion ausgewählt ist aus der Gruppe bestehend aus F-, Cl-, Br-, I-, ClO-, ClO2 -, ClO3 -, ClO4 -, OH-, NO3 -, NO2 -, SO4 2-, SO3 2-, PO4 3-, CO3 2-, CH3CO2 -, HCO2 - und CF3SO3 -, B4O7 2- und PF6 -;
    wobei mindestens eine organische verbindende Verbindung ein lineares ditopisches Carboxylat ist, aufweisend mindestens eine substituierte Phenylgruppe; und
    wobei das lineare ditopische Carboxylat ausgewählt ist aus der Gruppe bestehend aus:
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
     wobei die funktionale Gruppe X mindestens eine ist aus Wasserstoff, Amine, Halogenide, eine R-Gruppe, bestehend aus mindestens einem linearen, substituierten oder Cyklo- Alkane, Alkene, Alkine, Ketten und Ether O-R, ist, wobei R mindestens eine lineare substituierte oder Cyklo- Alkane, Alkene, Alkine, Ketten, und Mischungen davon.
  16. Das Verfahren, wie definiert in Anspruch 15, wobei X umfasst mindestens ein primäres, sekundäres oder tertiäres Amin; aromatisches Amin, Pyridin, Pyrimidin, wie 5 oder 6 gliedrige Ringe; Halogenide, beinhaltend substituierte -RX; Alkohole: ROH; Thiole: RSH; Sulfonate -R-SO3; Nitrogruppen -R(NO2); Phosphate -R-PO2-; Epoxide; Aldehyde (RCOH); Ketone (RCOR); Ester RCO2R; Carbonsäuren; Cycloalkene, Cykloalkine, Silylderivate; Boranderivate, Ferrocene, andere Metallocene, und Mischungen davon.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8071063B2 (en) 2008-02-21 2011-12-06 Exxonmobile Research And Engineering Company Separation of hydrogen from hydrocarbons utilizing zeolitic imidazolate framework materials
US8142746B2 (en) 2008-02-21 2012-03-27 Exxonmobil Research And Engineering Company Separation of carbon dioxide from methane utilizing zeolitic imidazolate framework materials
US8142745B2 (en) 2008-02-21 2012-03-27 Exxonmobil Research And Engineering Company Separation of carbon dioxide from nitrogen utilizing zeolitic imidazolate framework materials
CN104262400A (zh) * 2014-07-31 2015-01-07 华南理工大学 大孔容的多级孔道mil-101材料及制备方法和应用

Families Citing this family (205)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6754485B1 (en) * 1998-12-23 2004-06-22 American Calcar Inc. Technique for effectively providing maintenance and information to vehicles
EP1383775B1 (de) 2001-04-30 2006-08-02 The Regents of The University of Michigan Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung
US6893564B2 (en) 2002-05-30 2005-05-17 Basf Aktiengesellschaft Shaped bodies containing metal-organic frameworks
US7481866B2 (en) * 2002-06-19 2009-01-27 University Of Iowa Research Foundation Gas storage materials and devices
US7008607B2 (en) * 2002-10-25 2006-03-07 Basf Aktiengesellschaft Process for preparing hydrogen peroxide from the elements
US7039788B1 (en) * 2002-10-28 2006-05-02 Sandisk Corporation Method and apparatus for splitting a logical block
DE602004027036D1 (de) 2003-05-09 2010-06-17 Univ Michigan MOFs mit einer hohen Oberfläche und Methode zu deren Herstellung
US7309380B2 (en) * 2003-06-30 2007-12-18 Basf Aktiengesellschaft Gas storage system
US20050004404A1 (en) 2003-07-03 2005-01-06 Basf Akiengesellschaft Process for the alkoxylation of monools in the presence of metallo-organic framework materials
DE10355087A1 (de) 2003-11-24 2005-06-09 Basf Ag Verfahren zur elektrochemischen Herstellung eines kristallinen porösen metallorganischen Gerüstmaterials
JP2007518707A (ja) * 2003-12-05 2007-07-12 ザ リージェンツ オブ ザ ユニバーシティ オブ ミシガン 金属有機多面体
US7411081B2 (en) * 2004-01-13 2008-08-12 Basf Aktiengesellschaft Process for preparing and organometallic framework material
JP2006083898A (ja) * 2004-09-14 2006-03-30 Honda Motor Co Ltd 水素貯蔵タンク
CA2584912A1 (en) * 2004-10-22 2006-05-04 The Regents Of The University Of Michigan Covalently linked organic frameworks and polyhedra
US7524444B2 (en) * 2004-11-09 2009-04-28 Basf Aktiengesellschaft Shaped bodies containing metal-organic frameworks
US7343747B2 (en) 2005-02-23 2008-03-18 Basf Aktiengesellschaft Metal-organic framework materials for gaseous hydrocarbon storage
CA2604084A1 (en) * 2005-04-07 2006-10-19 The Regents Of The University Of Michigan High gas adsorption in a microporous metal-organic framework with open-metal sites
WO2006116340A1 (en) * 2005-04-22 2006-11-02 University Of South Florida Zeolite-like metal organic frameworks (zmofs): modular approach to the synthesis of organic-inorganic hybrid porous materials having a zeolite like topology
JP2008542722A (ja) * 2005-05-24 2008-11-27 ベイカー ヒューズ インコーポレイテッド 光音響分光法を使用した油層キャラクタリゼーションのための方法及び装置
DE102005023856A1 (de) 2005-05-24 2006-11-30 Basf Ag Verfahren zur Herstellung poröser metall-organischer Gerüstmaterialien
US8628055B2 (en) * 2005-07-27 2014-01-14 The Board Of Trustees Of The University Of Illinois Bi-direction rapid action electrostatically actuated microvalve
JP5292679B2 (ja) * 2005-08-05 2013-09-18 日産自動車株式会社 水素吸蔵材料である多孔性金属錯体の製造方法
JP5124918B2 (ja) * 2005-08-08 2013-01-23 トヨタ自動車株式会社 水素貯蔵装置
KR100979470B1 (ko) * 2005-08-08 2010-09-02 도요타 지도샤（주） 수소 저장장치
WO2007035596A2 (en) * 2005-09-19 2007-03-29 Mastertaste Inc. Metal organic framework odor sequestration and fragrance delivery
EP1770121B1 (de) * 2005-09-21 2008-10-01 The Goodyear Tire & Rubber Company Luftreifen umfassend eine Kautschukkomponente enthaltend ein zinkorganisches Gerüstmaterial
US7799120B2 (en) 2005-09-26 2010-09-21 The Regents Of The University Of Michigan Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room-temperature
CA2624959A1 (en) * 2005-10-06 2007-04-19 The Board Of Trustees Of The University Of Illinois High gain selective preconcentrators
US8123834B2 (en) * 2005-10-06 2012-02-28 The Board Of Trustees Of The University Of Illinois High gain selective metal organic framework preconcentrators
US8426337B2 (en) 2005-10-11 2013-04-23 The Regents Of The University Of Michigan Metal salt catalysts for enhancing hydrogen spillover
US7951749B2 (en) * 2005-10-11 2011-05-31 The Regents Of The University Of Michigan Enhancing hydrogen spillover and storage
US8338330B2 (en) * 2005-10-11 2012-12-25 The Regents Of The University Of Michigan Chemical bridges for enhancing hydrogen storage by spillover and methods for forming the same
DE102005054636A1 (de) * 2005-11-16 2007-05-24 Basf Ag Metallorganische Gerüstmaterialien der III. Nebengruppe
NZ569159A (en) * 2005-12-21 2010-11-26 Uop Llc The use of MOFS in pressure swing adsorption
CA2633652A1 (en) * 2005-12-21 2007-10-04 Uop Llc The use of mofs in pressure swing adsorption
CA2640300A1 (en) * 2006-02-10 2007-08-16 Basf Se Process for preparing porous organic frameworks
KR20080103986A (ko) 2006-02-10 2008-11-28 바스프 에스이 다공성 금속 유기 골격체 물질의 제조 방법
US8314245B2 (en) 2006-02-28 2012-11-20 The Regents Of The University Of Michigan Preparation of functionalized zeolitic frameworks
US8530649B2 (en) * 2006-03-08 2013-09-10 The University Of Tokyo Polymer complex
KR100806586B1 (ko) * 2006-03-10 2008-02-28 한국화학연구원 수분의 흡착 및 탈착을 위한 흡착제
GB2437063A (en) * 2006-04-10 2007-10-17 Uni I Oslo A process for oxide gas capture
US7880026B2 (en) * 2006-04-14 2011-02-01 The Board Of Trustees Of The University Of Illinois MOF synthesis method
KR20090031358A (ko) 2006-05-16 2009-03-25 바스프 에스이 다공질 금속 유기 골격체의 제조 방법
US7637983B1 (en) 2006-06-30 2009-12-29 Uop Llc Metal organic framework—polymer mixed matrix membranes
US7441574B2 (en) 2006-08-17 2008-10-28 The Goodyear Tire & Rubber Company Pneumatic tire
ATE452169T1 (de) 2006-10-20 2010-01-15 Consejo Superior Investigacion Stark hydrophobes lanthanid-organisches poröses material mit fluoreszenten und magnetischen eigenschaften
US20080111114A1 (en) * 2006-10-30 2008-05-15 Gilbert Alan M Flame-retardant materials and systems
US9017584B2 (en) * 2006-10-30 2015-04-28 Alan M. Gilbert Flame-retardant materials and systems
US9719019B1 (en) 2006-10-30 2017-08-01 Alan M. Gilbert Flame-retardant materials and systems
US7985868B1 (en) 2006-11-01 2011-07-26 Sandia Corporation Hybrid metal organic scintillator materials system and particle detector
US20080160356A1 (en) * 2006-12-08 2008-07-03 George Kisa Hayashi Shimizu Metal-Organic Solids for Use in Proton Exchange Membranes
FR2910457B1 (fr) * 2006-12-22 2009-03-06 Inst Francais Du Petrole Procede de purification par adsorption d'hydrogene avec cogeneration d'un flux de co2 en pression
KR101002571B1 (ko) 2007-01-03 2010-12-17 주식회사 인실리코텍 다공성 금속-유기 골격 구조를 갖는 배위중합체 결정 및이의 제조방법
US20100143693A1 (en) * 2007-01-24 2010-06-10 The Regents Of The University Of California Crystalline 3d- and 2d covalent organic frameworks
US7687432B2 (en) * 2007-02-02 2010-03-30 Miami University Mesh-adjustable molecular sieve
EP2155608A4 (de) * 2007-05-11 2011-01-12 Univ California Adsorptive gastrennung von mehrkomponentigen gasen
EP2150338B1 (de) * 2007-05-21 2013-02-27 Basf Se Aluminium-aminocarboxylate als poröse metallorganische gerüstmaterialien
EP2167511A4 (de) * 2007-07-17 2010-12-22 Univ California Herstellung von funktionalisierten zeolithrahmen
US9132411B2 (en) 2007-08-30 2015-09-15 The Regents Of The University Of Michigan Strategies, linkers and coordination polymers for high-performance sorbents
US8222179B2 (en) * 2007-08-30 2012-07-17 The Regents Of The University Of Michigan Porous coordination copolymers and methods for their production
US8383545B2 (en) * 2007-08-30 2013-02-26 The Regents Of The University Of Michigan Strategies, linkers and coordination polymers for high-performance sorbents
DE102008027218A1 (de) 2007-09-08 2009-03-12 Bayer Materialscience Ag Kobalt-basierte metallorganische Gerüstverbindungen
WO2009042802A1 (en) * 2007-09-25 2009-04-02 The Regents Of The University Of California Edible and biocompatible metal-organic frameworks
ES2345316B2 (es) 2007-09-28 2011-12-20 Ifp Metodo para la preparacion de esteres alcoholicos a partir de trigliceridos y alcoholes utilizando catalizadores heterogeneos basados en unsolido hibrido con una matriz mixta organica-inorganica.
FR2921661B1 (fr) * 2007-10-01 2013-05-31 Centre Nat Rech Scient Solide hybride organique inorganique a surface modifiee.
FR2921660B1 (fr) 2007-10-01 2015-09-25 Centre Nat Rech Scient Nanoparticules hybrides organiques inorganiques a base de carboxylates de fer.
WO2009046211A2 (en) * 2007-10-02 2009-04-09 The Regents Of The University Of Michigan Adsorbents for organosulfur compound removal from fluids
US20090126570A1 (en) * 2007-11-15 2009-05-21 Chunqing Liu Polymer Functionalized Molecular Sieve/Polymer Mixed Matrix Membranes
US8034952B2 (en) * 2007-11-15 2011-10-11 University Of South Florida Supramolecular assemblies and building blocks
US8425659B2 (en) * 2007-12-03 2013-04-23 The Regents Of The University Of Michigan Microporous coordination polymers as novel sorbents for gas separation
DE102008010774A1 (de) * 2007-12-21 2009-06-25 Cam-D Technologies Gmbh Grenzflächenaktive Metallkomplexe zur Adsorption von Schadstoffen sowie Verfahren zu ihrer Herstellung
DE102008010775A1 (de) * 2007-12-21 2009-06-25 Cam-D Technologies Gmbh Grenzflächenaktive Metallkomplexe auf Trägermaterialien zur Adsorption von Schadstoffen sowie Verfahren zur Herstellung der geträgerten Materialien
US8152908B2 (en) * 2008-01-16 2012-04-10 The Board Of Trustees Of The University Of Illinois Micromachined gas chromatography columns for fast separation of Organophosphonate and Organosulfur compounds and methods for deactivating same
DE102008007551A1 (de) 2008-02-05 2009-08-06 Bayer Materialscience Ag Metallorganische Gerüstverbindungen auf Basis von Triptycen
KR100980323B1 (ko) * 2008-02-22 2010-09-07 주식회사 엑스에프씨 수소저장장치
FR2929278A1 (fr) * 2008-04-01 2009-10-02 Centre Nat Rech Scient Solide hybride cristallin poreux pour l'adsorption et la liberation de gaz a interet biologique.
US8269029B2 (en) * 2008-04-08 2012-09-18 The Board Of Trustees Of The University Of Illinois Water repellent metal-organic frameworks, process for making and uses regarding same
KR101034988B1 (ko) * 2008-04-17 2011-05-17 한국화학연구원 유무기 혼성체 및 거대 메조세공 물질의 공유결합에 의하여 형성된 초다공성 유무기 나노세공 복합체
FR2931707B1 (fr) * 2008-05-30 2011-05-20 Inst Francais Du Petrole Systeme catalytique d'oligomerisation d'olefines a base de complexes organometalliques et de solide poreux.
US8946454B2 (en) * 2008-06-05 2015-02-03 The Regents Of The University Of California Chemical framework compositions and methods of use
KR20090131099A (ko) * 2008-06-17 2009-12-28 재단법인서울대학교산학협력재단 전자공여 아조그룹의 리간드를 포함하는 ＮｂＯ-망위상기하학적 구조의 영구 다공성 기체 저장용 금속-유기골격체 및 이를 포함하는 기체 저장체
FR2938540B1 (fr) 2008-11-18 2017-08-11 Centre Nat Rech Scient Procede de preparationhydrothermale de carboxylates d'aluminium poreux cristallises de type "metal-organic framework"
FR2938539B1 (fr) 2008-11-18 2012-12-21 Centre Nat Rech Scient Procede de preparation d'azocarboxylates aromatiques d'aluminium poreux et cristallises de type "metal-organic framework"
EP2358726B1 (de) 2008-12-18 2017-08-02 The Regents of the University of California Poröse reaktive rahmenwerke
US20110277767A1 (en) * 2008-12-18 2011-11-17 The Regents Of The University Of California Metal organic frameworks (mofs) for air purification
WO2010078337A1 (en) 2008-12-29 2010-07-08 The Regents Of The University Of California A gas sensor incorporating a porous framework
RU2393013C1 (ru) * 2009-01-11 2010-06-27 Государственное образовательное учреждение Высшего профессионального образования "Томский государственный университет" Способ получения металлорганического сорбента
WO2010083418A1 (en) 2009-01-15 2010-07-22 The Regents Of The University Of California Conductive organometallic framework
EP2384237A1 (de) 2009-02-02 2011-11-09 The Regents of The University of California Reversibles einfangen von ethylenoxid in porösen gerüsten
KR101029326B1 (ko) * 2009-02-03 2011-04-15 서울대학교산학협력단 큰 다공성의 금속-유기 골격체 및 이를 포함하는 가스 저장체 및 금속-유기 골격체 제조방법
US8324323B2 (en) * 2009-02-27 2012-12-04 Uop Llc Block coordination copolymers
US8884087B2 (en) * 2009-02-27 2014-11-11 Uop Llc Block coordination copolymers
US8309661B2 (en) * 2009-02-27 2012-11-13 Uop Llc Block coordination copolymers
BRPI1008306A2 (pt) * 2009-02-27 2017-03-28 Univ Michigan Regents copolímero de coordenação, processo usando um copolímero de coordenação, e, método para fabricar um copolímero de coordenação
US8389060B2 (en) * 2009-03-04 2013-03-05 Xerox Corporation Process for preparing structured organic films (SOFs) via a pre-SOF
US8322534B2 (en) * 2009-03-25 2012-12-04 Northwestern University Purification of metal-organic framework materials
US8449650B2 (en) * 2009-06-17 2013-05-28 Los Alamos National Security, Llc Gas storage and separation by electric field swing adsorption
CN102482294B (zh) 2009-06-19 2016-02-03 加利福尼亚大学董事会 复杂的混合配体开放骨架材料
WO2010148276A2 (en) 2009-06-19 2010-12-23 The Regents Of The University Of California Carbon dioxide capture and storage using open frameworks
EP2403815A1 (de) 2009-07-27 2012-01-11 The Regents of The University of California Oxidative homokupplungsreaktionen von arylborsäuren anhand einer porösen kupferbasierten metallorganischen struktur als heterogener hochleistungskatalysator
WO2011038208A2 (en) 2009-09-25 2011-03-31 The Regents Of The University Of California Open metal organic frameworks with exceptional surface area and high gas strorage capacity
RU2420352C1 (ru) * 2009-10-29 2011-06-10 Общество с ограниченной ответственностью "ЭНВАЙРОКЕТ" Адсорбент для улавливания, концентрирования и хранения co2
WO2011069541A1 (de) * 2009-12-09 2011-06-16 Technische Universität Bergakademie Freiberg Verfahren zur herstellung oxidbasierter metall-organischer gerüstmaterialien durch oxideinbau unter kontrolle des wassergehaltes
US20110138999A1 (en) * 2009-12-15 2011-06-16 Uop Llc Metal organic framework polymer mixed matrix membranes
US8859171B2 (en) 2010-03-03 2014-10-14 Xerox Corporation Charge transport particles
CN101890305B (zh) * 2010-04-01 2013-04-17 大连理工大学 一种金属有机框架膜的制备方法
WO2011123795A1 (en) 2010-04-02 2011-10-06 Battelle Memorial Institute Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, and gas separation assemblies
AU2010351979B2 (en) * 2010-04-30 2014-11-20 Commonwealth Scientific And Industrial Research Organisation Crystallisation facilitators for the synthesis of metal organic frameworks
US8157892B2 (en) 2010-05-17 2012-04-17 Enverid Systems, Inc. Method and system for improved-efficiency air-conditioning
US20110277490A1 (en) 2010-05-17 2011-11-17 Udi Meirav Method and System for Improved-Efficiency Air-Conditioning
US9567425B2 (en) 2010-06-15 2017-02-14 Xerox Corporation Periodic structured organic films
EP2585472A4 (de) 2010-07-20 2014-02-12 Univ California Funktionalisierung organischer moleküle mit metallorganischen rahmen (mofs) als katalysatoren
US8257889B2 (en) 2010-07-28 2012-09-04 Xerox Corporation Imaging members comprising capped structured organic film compositions
US8318892B2 (en) 2010-07-28 2012-11-27 Xerox Corporation Capped structured organic film compositions
US8697322B2 (en) 2010-07-28 2014-04-15 Xerox Corporation Imaging members comprising structured organic films
GB201013307D0 (en) 2010-08-09 2010-09-22 Univ St Andrews Anti-microbial metal organic framework
US8119314B1 (en) 2010-08-12 2012-02-21 Xerox Corporation Imaging devices comprising structured organic films
US8119315B1 (en) 2010-08-12 2012-02-21 Xerox Corporation Imaging members for ink-based digital printing comprising structured organic films
KR20140022362A (ko) 2010-09-27 2014-02-24 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 전도성 개방 골격체
EP2665733A4 (de) 2011-01-21 2014-07-30 Univ California Herstellung von metall-triazolat-rahmen
WO2012106451A2 (en) 2011-02-04 2012-08-09 The Regents Of The University Of California Preparation of metal-catecholate frameworks
US8690999B2 (en) * 2011-02-09 2014-04-08 Enverid Systems, Inc. Modular, high-throughput air treatment system
US8759473B2 (en) 2011-03-08 2014-06-24 Xerox Corporation High mobility periodic structured organic films
EP2691171B1 (de) * 2011-03-31 2019-07-03 Council of Scientific & Industrial Research Verbundstoffe aus cu-btc metallorganischen gerüstmaterialien mit aktiviertem kohlenstoff mit erhöhter gasadsorptionskapazität und verfahren zu ihrer herstellung
CN108579706A (zh) 2011-05-17 2018-09-28 恩弗里德系统公司 用于从室内空气降低二氧化碳的吸着剂
US8247142B1 (en) 2011-06-30 2012-08-21 Xerox Corporation Fluorinated structured organic film compositions
US8353574B1 (en) 2011-06-30 2013-01-15 Xerox Corporation Ink jet faceplate coatings comprising structured organic films
US9353129B2 (en) 2011-07-06 2016-05-31 The Regents Of The University Of Michigan Microporous coordination complex and method of making the same
WO2013058844A1 (en) * 2011-07-06 2013-04-25 Northwestern University System and method for generating and/or screening potential metal-organic frameworks
US9012368B2 (en) 2011-07-06 2015-04-21 Northwestern University System and method for generating and/or screening potential metal-organic frameworks
JP6049712B2 (ja) 2011-07-08 2016-12-21 ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒルＴｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｎｏｒｔｈ Ｃａｒｏｌｉｎａ Ａｔ Ｃｈａｐｅｌ Ｈｉｌｌ 抗癌治療及び画像化並びに骨障害治療のための金属ビスホスホネートナノ粒子
US8313560B1 (en) 2011-07-13 2012-11-20 Xerox Corporation Application of porous structured organic films for gas separation
US8410016B2 (en) 2011-07-13 2013-04-02 Xerox Corporation Application of porous structured organic films for gas storage
US8377999B2 (en) 2011-07-13 2013-02-19 Xerox Corporation Porous structured organic film compositions
CN103827123A (zh) * 2011-09-02 2014-05-28 德克萨斯A&M大学系统 包含用于小分子捕获的内置式单分子阱的多孔材料
US8460844B2 (en) 2011-09-27 2013-06-11 Xerox Corporation Robust photoreceptor surface layer
US8372566B1 (en) 2011-09-27 2013-02-12 Xerox Corporation Fluorinated structured organic film photoreceptor layers
EP2766046B1 (de) 2011-10-13 2017-08-02 The Regents of The University of California Metallorganische gerüste mit aussergewöhnlich grossporigen öffnungen
US10139169B2 (en) 2011-10-21 2018-11-27 Massachusetts Institute Of Technology Adsorption system
CN103084209B (zh) * 2011-10-27 2014-12-10 中国科学院大连化学物理研究所 一种镍基微孔材料在催化酯化反应中的应用
CN103086867B (zh) * 2011-10-27 2015-12-16 中国科学院大连化学物理研究所 一种镍基微孔材料及其制备方法
WO2013074973A1 (en) 2011-11-17 2013-05-23 Enverid Systems, Inc. Method and system for conditioning air in an enclosed environment with distributed air circuilatioin systems
CN107339779B (zh) 2012-01-10 2020-02-18 恩弗里德系统公司 用于管理空调系统中的空气质量和能量使用的方法和系统
US8529997B2 (en) 2012-01-17 2013-09-10 Xerox Corporation Methods for preparing structured organic film micro-features by inkjet printing
WO2013158484A1 (en) 2012-04-18 2013-10-24 King Abdullah University Of Science And Technology Electrode separator
US9562649B2 (en) 2012-04-25 2017-02-07 Saudi Arabian Oil Company Adsorbed natural gas storage facility
CN104379234B (zh) 2012-05-22 2018-02-27 恩沃德系统公司 对室内空气的洗涤的吸附剂的高效利用
JP2015528743A (ja) 2012-07-18 2015-10-01 エンベリッド システムズ， インコーポレイテッド 屋内空気清浄のための再生吸収剤
US9604195B2 (en) * 2012-08-10 2017-03-28 University Of South Florida Metal-organic materials (MOMs) for CO2 adsorption and methods of using MOMs
US9138719B1 (en) * 2012-08-10 2015-09-22 University Of South Florida Metal-organic materials (MOMs) for CO2 adsorption and methods of using MOMs
US8765340B2 (en) 2012-08-10 2014-07-01 Xerox Corporation Fluorinated structured organic film photoreceptor layers containing fluorinated secondary components
CN104685300B (zh) 2012-09-24 2017-11-28 恩沃德系统公司 具有集成空气处理的空气处理系统
PL228519B1 (pl) 2012-10-05 2018-04-30 Inst Chemii Fizycznej Polskiej Akademii Nauk Sposób otrzymywania materiałów porowatych typu MOF
WO2014078708A1 (en) 2012-11-15 2014-05-22 Enverid Systems, Inc. Method and system for reduction of unwanted gases in indoor air
US8883676B1 (en) * 2013-01-08 2014-11-11 The United States Of America As Represented By The Secretary Of The Army Removal of toxic chemicals using metal-organic frameworks (MOFs) post-treated via plasma-enhanced chemical vapor deposition (PECVD) with fluorocarbons
US8906462B2 (en) 2013-03-14 2014-12-09 Xerox Corporation Melt formulation process for preparing structured organic films
CN104164228A (zh) * 2013-05-15 2014-11-26 宁波大学 一种基于irmof-3功能材料的修饰与制备方法
CN104164227A (zh) * 2013-05-15 2014-11-26 宁波大学 一系列金属有机主客体复合材料的制备方法与性能
US9919257B2 (en) 2013-09-17 2018-03-20 Enverid Systems, Inc. Systems and methods for efficient heating of sorbents in an indoor air scrubber
CN104549454B (zh) * 2013-10-28 2017-06-20 中国石油化工股份有限公司 原位合成的含氧化合物芳构化催化剂及其制备方法
WO2015066693A1 (en) 2013-11-04 2015-05-07 The Regents Of Thd University Of California Metal-organic frameworks with a high density of highly charged exposed metal cation sites
GB201414117D0 (en) 2013-11-26 2014-09-24 Texas A & M Univ Sys Titanium metal organic framework materials
EP3074404B1 (de) 2014-02-19 2020-01-01 The Regents of The University of California Säure, lösungsmittel und wärmebeständige metallorganische gerüste
KR20160134644A (ko) 2014-03-18 2016-11-23 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 미세다공성 금속 유기 구조체의 정렬된 초격자로 구성된 메조스코픽 물질
WO2015195179A2 (en) 2014-03-28 2015-12-23 The Regents Of The University Of California Metal organic frameworks comprising a plurality of sbus with different metal ions and/or a plurality of organic linking ligands with different functional groups.
EP3206987B2 (de) 2014-10-14 2024-07-24 The University of Chicago Nanopartikel zur fotodynamischen therapie, röntgeninduzierte fotodynamische therapie, radiotherapie, chemotherapie, immuntherapie und kombinationen davon
US10806694B2 (en) 2014-10-14 2020-10-20 The University Of Chicago Nanoparticles for photodynamic therapy, X-ray induced photodynamic therapy, radiotherapy, radiodynamic therapy, chemotherapy, immunotherapy, and any combination thereof
CN104310522B (zh) * 2014-10-30 2016-01-06 东华理工大学 一种超痕量Hg(Ⅱ)去除方法
US10118877B2 (en) 2014-12-03 2018-11-06 The Regents Of The University Of California Metal-organic frameworks for aromatic hydrocarbon separations
DK3253485T3 (da) 2015-02-03 2022-03-21 Univ Court Univ St Andrews No-holdige sammensætninger
CN107708838A (zh) 2015-05-11 2018-02-16 恩弗里德系统公司 减少室内空气多余气体的方法和系统
US10058855B2 (en) 2015-05-14 2018-08-28 The Regents Of The University Of California Redox-active metal-organic frameworks for the catalytic oxidation of hydrocarbons
US10201803B2 (en) 2015-06-09 2019-02-12 The Regents Of The University Of California Polymer-metal organic framework materials and methods of using the same
US20170036993A1 (en) * 2015-08-07 2017-02-09 Eastman Chemical Company Metal-organic framework for fluid stream filtration applications
US10792608B2 (en) 2015-08-24 2020-10-06 Enverid Systems, Inc. Scrubber for HVAC system
CN108473325A (zh) 2015-11-27 2018-08-31 加利福尼亚大学董事会 沸石咪唑酯框架
KR20180088422A (ko) 2015-11-27 2018-08-03 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 직조된 공유결합성 유기 골격체
WO2017152240A1 (en) 2016-03-11 2017-09-14 Commonwealth Scientific And Industrial Research Organisation Polymeric agents and compositions for inhibiting corrosion
US11207633B2 (en) 2016-04-19 2021-12-28 Enverid Systems, Inc. Systems and methods for closed-loop heating and regeneration of sorbents
WO2017201528A1 (en) 2016-05-20 2017-11-23 The University Of Chicago Nanoparticles for chemotherapy, targeted therapy, photodynamic therapy, immunotherapy, and any combination thereof
US10472299B2 (en) 2016-06-24 2019-11-12 The Regents Of The University Of Michigan Explosive microporous coordination polymers
WO2018022944A1 (en) 2016-07-27 2018-02-01 Massachusetts Institute Of Technology BLOCK CO-POLY(METAL ORGANIC NANOSTRUCTURES) (BCPMONs) AND USES THEREOF
US10961338B2 (en) 2016-08-26 2021-03-30 Massachusetts Institute Of Technology Bottlebrush polymers and uses thereof
CN106478959B (zh) * 2016-09-23 2019-05-28 肇庆学院 一种基于4,4’-二羧基二苯醚的Cd-MOF及其制备方法
WO2018067702A1 (en) 2016-10-04 2018-04-12 Massachusetts Institute Of Technology Bottlebrush copolymers and uses thereof
WO2018089856A1 (en) 2016-11-10 2018-05-17 Enverid Systems, Inc. Low noise, ceiling mounted indoor air scrubber
US11752221B2 (en) 2017-06-30 2023-09-12 Massachusetts Institute Of Technology Brush-arm star polymer imaging agents and uses thereof
WO2019006426A2 (en) 2017-06-30 2019-01-03 Massachusetts Institute Of Technology RAMIFIED MULTIFUNCTIONAL MACROMONOMERS AND RELATED POLYMERS AND USES THEREOF
CN111194232B (zh) 2017-08-02 2023-01-31 芝加哥大学 纳米级金属有机层和金属有机纳米片
WO2019060818A2 (en) * 2017-09-25 2019-03-28 Numat Technologies, Inc. HIGHLY REACTIVE GAS STABILIZATION ASSISTED BY ADSORBENT
US11724241B2 (en) 2018-02-15 2023-08-15 Cambridge Enterprise Limited Constant shear continuous reactor device
US12414997B2 (en) 2018-04-13 2025-09-16 Massachusetts Institute Of Technology Brush prodrugs and uses thereof
GB201813439D0 (en) 2018-08-17 2018-10-03 Univ Tartu Novel catalytic materials
WO2020037236A1 (en) 2018-08-17 2020-02-20 Massachusetts Institute Of Technology Degradable polymers of a cyclic silyl ether and uses thereof
US20200155684A1 (en) * 2018-11-20 2020-05-21 The Regents Of The University Of Michigan Compositions and methods for delivering pharmaceutical agents
US12478683B2 (en) 2019-10-16 2025-11-25 Massachusetts Institute Of Technology Brush prodrugs and uses thereof
CN113117751B (zh) * 2019-12-31 2023-05-05 中国石油化工股份有限公司 一种金属有机骨架复合材料及其制备方法
US12042513B2 (en) 2020-01-10 2024-07-23 Massachusetts Institute Of Technology Proteolysis targeting chimeric molecules (PROTACs) with functional handles and uses thereof
CN116099011B (zh) * 2020-04-24 2024-12-24 中国科学院精密测量科学与技术创新研究院 一种irmof-8或irmof-10在常温条件下在超灵敏磁共振成像中的应用
US20230178848A1 (en) 2020-04-28 2023-06-08 King Abdullah University Of Science And Technology Electrode separators
CN113045460A (zh) * 2021-03-08 2021-06-29 福建师范大学 一种高核水簇的氢键有机框架材料及其制备方法
WO2023121753A1 (en) 2021-12-20 2023-06-29 Massachusetts Institute Of Technology Biomolecule-polymer-pharmaceutical agent conjugates for delivering the pharmaceutical agent
CN114708922A (zh) * 2022-04-26 2022-07-05 广州大学 一种有机框架设计方法、装置、电子设备和存储介质
KR20240012012A (ko) * 2022-07-20 2024-01-29 숙명여자대학교산학협력단 세척 공정 없이 불순물이 적은 금속-유기 골격체의 제조방법 및 금속-유기 골격체
EP4638544A1 (de) 2022-12-23 2025-10-29 Basf Se Verfahren zur herstellung von polyacetalpolyolen und deren verwendung in pu-systemen

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3144418A (en) 1959-08-17 1964-08-11 Union Carbide Corp Polymerization of epoxides
DE69306607D1 (de) 1992-02-20 1997-01-30 Arco Chem Tech Reinigung von niedrigem Alkylenoxyd
DE4408772B4 (de) 1993-03-16 2006-09-07 Mitsubishi Chemical Corp. Verfahren zur Herstellung eines Polyoxyalkylenglykols und neues Metallaluminosilikat
AU692041B2 (en) 1995-02-13 1998-05-28 Osaka Gas Co., Ltd. Gas storage apparatus, gaseous fuel automobile using the gasstorage apparatus, gas storage method and methane adsorbing-retaining agent
US5648508A (en) 1995-11-22 1997-07-15 Nalco Chemical Company Crystalline metal-organic microporous materials
US5780233A (en) 1996-06-06 1998-07-14 Wisconsin Alumni Research Foundation Artificial mismatch hybridization
DE19723950A1 (de) 1997-06-06 1998-12-10 Basf Ag Verfahren zur Oxidation einer mindestens eine C-C-Doppelbindung aufweisenden organischen Verbindung
US6372932B1 (en) * 1997-07-25 2002-04-16 University Of Liverpool Porous solid products of 1,3,5-benzenetricarboxylate and metal ions
US6312902B1 (en) 1998-03-13 2001-11-06 Promega Corporation Nucleic acid detection
DE19835907A1 (de) 1998-08-07 2000-02-17 Basf Ag Verfahren zur Umsetzung einer organischen Verbindung mit einem Hydroperoxid
JP3985114B2 (ja) * 1998-10-05 2007-10-03 大阪瓦斯株式会社 新規三次元型有機金属錯体及びガス吸着材
DE19847629A1 (de) 1998-10-15 2000-04-20 Basf Ag Verfahren zur Oxidation einer mindestens eine C-C-Doppelbindung aufweisenden organischen Verbindung
DE19928156A1 (de) 1999-06-19 2000-12-28 Bayer Ag Aus Polyetherpolyolen hergestellte Polyurethan-Weichschäume
DE19936547A1 (de) 1999-08-04 2001-02-15 Basf Ag Verfahren zur Umsetzung einer organischen Verbindung mit einem Hydroperoxid
DE19941242A1 (de) 1999-08-31 2001-03-08 Basf Ag Polyetheralkohole
DE19949092A1 (de) 1999-10-12 2001-04-19 Basf Ag Verfahren zur Herstellung von Polyetheralkoholen
DE10015246A1 (de) 2000-03-28 2001-10-04 Basf Ag Verfahren zur Umsetzung einer organischen Verbindung mit einem Hydroperoxid
DE10032885A1 (de) 2000-07-06 2002-01-17 Basf Ag Verfahren zur Herstellung von Propylenoxid
DE10032884A1 (de) 2000-07-06 2002-01-24 Basf Ag Verfahren zur Herstellung von Propylenoxid
DE10111230A1 (de) 2001-03-08 2002-09-19 Basf Ag Metallorganische Gerüstmaterialien und Verfahren zu deren Herstellung
EP1383775B1 (de) * 2001-04-30 2006-08-02 The Regents of The University of Michigan Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung
EP1280090A1 (de) 2001-07-27 2003-01-29 iSenseIt AG Verfahren zur Konfiguration paralleler Nukleinsäureanalyseverfahren
DE10143195A1 (de) 2001-09-04 2003-03-20 Basf Ag Integriertes Verfahren zur Herstellung von Polyurethan-Schäumen
US20030078311A1 (en) 2001-10-19 2003-04-24 Ulrich Muller Process for the alkoxylation of organic compounds in the presence of novel framework materials
KR20030042581A (ko) 2001-11-23 2003-06-02 삼성전자주식회사 대립유전자－특이적 프라이머 연장반응에서 프라이머간의 식별을 증가시키는 방법
US6929679B2 (en) 2002-02-01 2005-08-16 Basf Aktiengesellschaft Method of storing, uptaking, releasing of gases by novel framework materials
JP2004024247A (ja) 2002-04-30 2004-01-29 Internatl Reagents Corp 遺伝子変異検出用プローブ及び遺伝子変異検出方法
US6624318B1 (en) 2002-05-30 2003-09-23 Basf Aktiengesellschaft Process for the epoxidation of an organic compound with oxygen or an oxygen-delivering compounds using catalysts containing metal-organic frame-work materials
US6893564B2 (en) 2002-05-30 2005-05-17 Basf Aktiengesellschaft Shaped bodies containing metal-organic frameworks
US7008607B2 (en) 2002-10-25 2006-03-07 Basf Aktiengesellschaft Process for preparing hydrogen peroxide from the elements
US6617467B1 (en) 2002-10-25 2003-09-09 Basf Aktiengesellschaft Process for producing polyalkylene carbonates
US7309380B2 (en) 2003-06-30 2007-12-18 Basf Aktiengesellschaft Gas storage system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8071063B2 (en) 2008-02-21 2011-12-06 Exxonmobile Research And Engineering Company Separation of hydrogen from hydrocarbons utilizing zeolitic imidazolate framework materials
US8142746B2 (en) 2008-02-21 2012-03-27 Exxonmobil Research And Engineering Company Separation of carbon dioxide from methane utilizing zeolitic imidazolate framework materials
US8142745B2 (en) 2008-02-21 2012-03-27 Exxonmobil Research And Engineering Company Separation of carbon dioxide from nitrogen utilizing zeolitic imidazolate framework materials
US8192709B2 (en) 2008-02-21 2012-06-05 Exxonmobil Research And Engineering Company Separation of methane from higher carbon number hydrocarbons utilizing zeolitic imidazolate framework materials
CN104262400A (zh) * 2014-07-31 2015-01-07 华南理工大学 大孔容的多级孔道mil-101材料及制备方法和应用
CN104262400B (zh) * 2014-07-31 2017-02-01 华南理工大学 大孔容的多级孔道mil‑101材料及制备方法和应用

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